Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof

Definitions

• the present invention relates to a process for the preparation of para acyloxybenzenesulfonates. It relates more particularly to the preparation by acid catalysis of para acyloxybenzenesulfonates in which the acyloxy group contains between 7 and 12 carbon atoms.
• M is an alkali, alkaline earth metal or an ammonium group is characterized in that an alkali, alkaline earth or ammonium phenolsulfonate is acylated by the anhydride of an acid containing 7 to 12 carbon atoms, linear or branched, in a polar aprotic solvent in the presence of a catalytic amount of sulfonic acid.
• the present invention is particularly well suited to acid anhydrides containing nine carbon atoms.
• these anhydrides are particularly concerned pelargonic anhydrides and 3,5,5 trimethylhexanoic because they are available industrially.
• the acid anhydrides can be prepared in a known manner by several methods. According to a first form of implementation described in “Organic collective synthesis” John Wiley, 1955 volume 3 p. 28, the acid chloride, the acid and a tertiary base can be brought into contact which will neutralize the acid formed. The desired anhydride and a tertiary base hydrochloride are thus obtained. According to a second form of implementation described in "Journal of Chemical Society” 1964 p. 755, the acid chloride and the sodium salt of the acid can be contacted in water. The desired anhydride and sodium chloride are thus obtained. As this reaction takes place in water, the anhydride formed must not be easily hydrolyzable.
• the acetic anhydride is reacted with the acid according to the following mechanism:
• phenolsulfonates in which R 2 is hydrogen and very particularly the sodium and potassium phenol sulfonate since they are those which are most readily available industrially.
• the solvent must nevertheless be odorless since it is impossible from a commercial point of view to incorporate into a detergent mixture a smelly product.
• the solvent must have a boiling point not too high and it must be of a cost price low enough not to unnecessarily increase the price of the product to be obtained.
• dimethylformamide is the one that best meets these conditions.
• the sulphonic acid used as catalyst for the condensation reaction corresponds to the following general formula: in which R 3 represents hydrogen, an alkyl radical containing from 1 to 12 carbon atoms, halo alkyl, phenyl, alkylphenyl, nitro, halo, SO 3 M.
• the acid chosen must be a strong acid but not oxidizing so as to avoid any coloring of the product obtained.
• Paratoluenesulfonic acid is preferably used.
• the molar ratio of solvent to phenolsulfonate is preferably between 5 and 50. A greater amount is not excluded from the scope of the invention, but the amounts will have to be adapted to the economy of the process; more preferably, this molar ratio is between 5 and 10 and even more preferably this ratio is between 7 and 10.
• the molar ratio of sulfonic acid to phenol sulfonate is preferably greater than about 0.01 and preferably about 0.02.
• the reaction temperature influences the reaction rate so a temperature above 100 ° C is advantageous, beyond 125 ° C side reactions appear between the anhydride and the solvent especially in the case of dimethylformamide with formation of amides which significantly reduce yields.
• the preferred reaction temperature is therefore between 110 and 120 ° C.
• the reaction is generally carried out at atmospheric pressure although a higher pressure is not harmful to the process of the invention.
• the products according to the invention can be extracted from the reaction medium by salting out with acetone, at a temperature equal to or greater than 90 ° C. by adding approximately the same weight of acetone as that of the solvent introduced.
• Para acyloxybenzenesulfonates are used in detergents as surfactants.
• Examples of compounds of formula (I) that may be mentioned sodium trimethyl-3,5,5 hexanoyloxy-benzenesulfonate, sodium octanoylbenzenesulfonate, sodium dodecanoyloxybenzenesulfonate.
• the reaction medium is brought to 160 ° C (under 1300 Pa) to remove the excess acetic anhydride.
• reaction medium is brought to 115 ° C. and 596 kg of T.M.H anhydride (30% excess) are introduced in half an hour to three quarter of an hour.
• the temperature is maintained for 6 hours without exceeding 120 ° C. in order to avoid the DMF decomposition reaction.
• the ester is filtered on a 6 m 2 surface filter working under pressure.
• the solutions are distilled and recycled.
• Octanoic anhydride is produced under the same conditions as in the previous example.
• reaction medium is brought to 115 ° C. and 342 kg of octanoic anhydride (40% excess) are added in half an hour.
• the reaction is finished after 5 hours.
• the product is filtered.
• Example 1 The conditions of Example 1 were repeated, replacing the paratoluenesulfonic acid with metanitrobenzenesulfonic acid (2 kg).
• Example 1 The reaction conditions of Example 1 were repeated, replacing the paratoluenesulfonic acid with benzenesulfonic acid (2 kg).
• Dodecanoic anhydride is produced under the same conditions as Example 1.
• the reaction medium is left at 115 ° C for 5 hours.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Medicines Containing Plant Substances (AREA)
• Saccharide Compounds (AREA)
• Medicines Containing Material From Animals Or Micro-Organisms (AREA)
• Silicon Polymers (AREA)
• Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

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• 1984
  • 1984-02-17 FR FR8402398A patent/FR2559768B1/fr not_active Expired
• 1985
  • 1985-02-08 DE DE8585400208T patent/DE3560032D1/de not_active Expired
  • 1985-02-08 EP EP85400208A patent/EP0153222B1/de not_active Expired
  • 1985-02-08 AT AT85400208T patent/ATE24313T1/de not_active IP Right Cessation
  • 1985-02-15 NO NO850593A patent/NO160134C/no unknown
  • 1985-02-15 GR GR850408A patent/GR850408B/el unknown
  • 1985-02-15 ES ES540435A patent/ES8602628A1/es not_active Expired
  • 1985-02-15 FI FI850636A patent/FI80672C/fi not_active IP Right Cessation
  • 1985-02-15 DK DK71485A patent/DK71485A/da not_active Application Discontinuation
  • 1985-02-15 JP JP60026637A patent/JPS60202856A/ja active Granted
  • 1985-02-15 BR BR8500715A patent/BR8500715A/pt unknown
  • 1985-02-19 US US06/702,733 patent/US4588532A/en not_active Expired - Fee Related

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